Pore phase change material cell fabricated from recessed pillar

ABSTRACT

A method of manufacturing an electrode is provided that includes providing a pillar of a first phase change material atop a conductive structure of a dielectric layer; or the inverted structure; forming an insulating material atop dielectric layer and adjacent the pillar, wherein an upper surface of the first insulating material is coplanar with an upper surface of the pillar; recessing the upper surface of the pillar below the upper surface of the insulating material to provide a recessed cavity; and forming a second phase change material atop the recessed cavity and the upper surface of the insulating material, wherein the second phase change material has a greater phase resistivity than the first phase change material.

FIELD OF THE INVENTION

In one embodiment, the present invention relates to memory devices.

BACKGROUND OF THE INVENTION

Phase change memory (PCM) devices store data using a phase changematerial, such as, for example, a chalcogenide alloy, that transformsinto a crystalline state or an amorphous state. An electrode may providea current to the PCM device to produce heat that effectuates phasechanges in PCM between crystalline and amorphous phases. Each state ofthe phase change material has different resistance characteristics.Specifically, the phase change material in the crystalline state has lowresistance and the phase change material in the amorphous state has highresistance. The crystalline state is typically referred to as a “setstate” having a logic level “0”, and the amorphous state is typicallyreferred to as a Preset states having a logic level “1”.

SUMMARY OF THE INVENTION

The present invention, in one aspect provides a memory device having afirst phase change material of a first resistivity in direct physicalcontact, i.e., in abutting relationship, with a second phase changematerial of a second resistivity. In one embodiment, the first phasechange material having the first resistivity is positioned on the secondphase change material having the second resistivity, wherein a barriermetal is positioned at the interface of the first phase change materialand the second phase change material. In one embodiment, the first phasechange material may remain in a low conductivity crystalline state toprovide at least a portion of a thermally insulated sublithographicelectrode that contributes to minimize the reset power of the device.

In one embodiment, the memory device includes:

a first phase change material; and

a second phase change material comprising a first portion positioned onthe first phase change material and having a first width substantiallyequal to a width of the first phase change material, and a secondportion having a second width greater than the first width, wherein thesecond phase change material has a greater phase resistivity than thefirst phase change material.

In one embodiment, the first phase change material is in direct physicalcontact with the second phase change material. In another embodiment, aninterface barrier metal is positioned between, i.e., positioned on, thefirst phase change material and the second phase change material. Theinterface barrier metal may be in direct physical contact with at leastone of the first phase change material and the second phase changematerial. In one embodiment, the interface barrier metal is in directphysical contact with both of the first and the second phase changematerials.

In one embodiment of the memory device, the first phase change materialand the second phase change material are composed of a materialincluding Ge, Sb, or Te or a combination thereof. In one embodiment, thefirst phase change material is of high purity and the second phasechange material is doped. In one embodiment, the first phase changematerial is composed of pure Ge₂Sb₂Te₅, and the second phase changematerial is composed of G₂Sb₂Te₅ doped with a nitride, oxide, oroxynitride dopant. In one embodiment, the first portion of the secondphase change material is in direct physical contact with the first phasechange material. In another embodiment, an interposed barrier metalseparates the first phase change material from the first portion of thesecond phase change material.

In one embodiment, the first width of the first portion of the secondphase change material ranges from about 0 nm to about 50 nm, and thesecond width of the second portion of the second phase change materialportion ranges from about 10 nm to about 50 nm. In one embodiment, thesecond portion of the second phase change material may further include athird width, wherein the third width of the second portion of the secondphase change material is greater than the second width of the secondportion of the second phase change material. In one embodiment, theresistivity of the amorphous phase of the second phase change materialis greater than the resistivity of the amorphous phase of the firstphase change material. In one embodiment, the resistivity of thecrystalline phase of the second phase change material is greater thanthe resistivity of the crystalline phase of the first phase changematerial. In one embodiment, the resistivity of the first phase changematerial ranges from about 10⁻⁶ ohm-m to about 10² ohm-m, and theresistivity of the second phase change material ranges from about 10⁻²ohm-m to about 10⁺⁵ ohm-m.

In another aspect, the present invention provides a method of forming amemory device. In one embodiment, the inventive method of forming amemory device includes:

providing a pillar of at least a first phase change material positionedon a conductive structure positioned in a dielectric layer;

forming an insulating material abutting the pillar of the first phasechange material and atop the conductive structure, wherein an uppersurface of the insulating material is coplanar with an upper surface ofthe pillar;

recessing the upper surface of the pillar below the upper surface of theinsulating material to provide a recessed pillar; and

forming a second phase change material atop the recessed pillar and theupper surface of the insulating material, wherein the second phasechange material has a greater phase resistivity than the first phasechange material.

In one embodiment, the pillar further includes an interface barriermetal positioned on an upper surface of the first phase change material.In one embodiment, the interface barrier metal is in direct physicalcontact with the first and the second phase change materials. In oneembodiment of the method for forming a memory device, the pillar mayhave a width that is less than the width of the conductive structure. Inone embodiment, the pillar may further include a first barrier metalpositioned between, i.e. positioned on, the first phase change materialand the conductive structure. In another embodiment, the first barriermetal is in direct physical contact with the upper surface of theconductive structure and the lower surface of the first phase changematerial. In another embodiment, a second barrier metal is positioned onthe upper surface of the second phase change material. In oneembodiment, the second barrier metal is in direct physical contact withthe upper surface of the second phase change material. In oneembodiment, the conductive structure may be a metal stud composed of W,and the first and second barrier metal of the pillar may be composed ofTiN or TaN.

In one embodiment, the step of providing the pillar includes depositinga layer of the first barrier metal atop the conductive structure and thedielectric layer; depositing a layer of the first phase change materialatop the layer of the first barrier metal; forming a block mask atop aportion of the layer of the first phase change material, wherein aremaining portion of the layer of the first phase change material isexposed; trimming the block mask to achieve sublithographic dimensions;removing the remaining portion of the layer of the first phase changematerial and the portions the first barrier metal underlying theremaining portion of the layer of the first phase change material withan anisotropic etch step; and removing the block mask. In oneembodiment, the first phase change material is composed of pureGe₂Sb₂Te₅. In another embodiment, the step of providing the pillarincludes depositing an interface barrier metal atop the first phasechange material.

In one embodiment, the step of recessing the upper surface of the pillarincludes etching the first phase change material selective to theinsulating material until the upper surface of the pillar is recessed toa depth below the upper surface of the insulating material resulting inthe formation of a cavity. In another embodiment when an interfacebarrier metal is positioned on the first phase change material, the stepof recessing the upper surface of the pillar includes etching theinterface barrier metal selectively to the insulating material until theupper surface of the interface barrier metal is recessed to a depthbelow the upper surface of the insulating material resulting in theformation of a cavity. In one embodiment, the upper surface of thepillar may be recessed to a depth ranging from about 0 nm to about 50 nmfrom the upper surface of the insulating material.

In one embodiment, the step of forming the second phase change materialatop the recessed pillar and the upper surface of the insulatingmaterial includes depositing a first layer of the second phase changematerial atop the recessed pillar and the insulating material;planarizing the first layer of the second phase change material until anupper surface of the second phase change material within the cavity iscoplanar with the upper surface of the insulating material; anddepositing a second layer of the phase change material atop the uppersurface of the second phase change material within the cavity and theupper surface of the insulating material. In one embodiment, the secondphase change material is composed of Ge₂Sb₂Te₅ doped with a nitride,oxide, or oxynitride dopants.

BRIEF DESCRIPTION OF THE DRAWINGS

The following detailed description, given by way of example and notintended to limit the invention solely thereto, will best be appreciatedin conjunction with the accompanying drawings, wherein like referencenumerals denote like elements and parts, in which:

FIG. 1A is a side cross sectional view depicting one embodiment of aphase change memory device including a memory cell having a first changematerial in direct physical contact with a second phase change material,in accordance with the present invention.

FIG. 1B is a side cross sectional view depicting one embodiment of aphase change memory device including a memory cell having an interfacebarrier metal positioned between, i.e., positioned on, a first phasechange material and a second phase change material, in accordance withthe present invention.

FIG. 1C is a side cross sectional view depicting one embodiment of aphase change memory device including a memory cell having a firstportion of a first phase change material and a second portion of asecond phase change material, in which the entire second portion of asecond phase change material has a width that is substantially equal tothe entire first portion of the first phase change material, inaccordance with the present invention.

FIG. 2A is a side cross sectional view of one embodiment of an initialstructure including a layer of dielectric material having at least oneconductive structure; and a stack atop the initial structure including alayer of a first barrier metal and a layer of a first phase changematerial, as used in accordance with the present invention.

FIG. 2B is a side cross sectional view depicting one embodiment of aninitial structure including a layer of dielectric material having atleast one conductive structure; and a stack atop the initial structureincluding a layer of a first barrier metal positioned on an uppersurface of the initial structure, a layer of a first phase changematerial positioned on the layer of the first barrier metal, and a layerof an interface barrier metal positioned on the layer of the first phasechange material, as used in accordance with the present invention.

FIG. 3 is a side cross sectional view depicting a structure followingthe patterning of the stack to provide a pillar; and the forming of thefirst insulating layer having an upper surface co-planar with the uppersurface of the pillar, in accordance with one embodiment of the presentinvention.

FIG. 4 is a side cross sectional view depicting recessing the firstphase change material below an upper surface of the insulating material,in accordance with one embodiment of the present invention.

FIG. 5 is a side cross sectional view depicting one embodiment of aforming a second phase change material atop a recessed first phasechange material and atop the upper surface of the insulating material,in accordance with the present invention.

FIG. 6 is a side cross sectional view depicting the formation ofelectrodes to the phase change memory device, in accordance with oneembodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Detailed embodiments of the present invention are disclosed herein;however, it is to be understood that the disclosed embodiments aremerely illustrative of the invention that may be embodied in variousforms. In addition, each of the examples given in connection with thevarious embodiments of the invention are intended to be illustrative,and not restrictive. Further, the figures are not necessarily to scale,some features may be exaggerated to show details of particularcomponents. Therefore, specific structural and functional detailsdisclosed herein are not to be interpreted as limiting, but merely as arepresentative basis for teaching one skilled in the art to variouslyemploy the present invention.

The embodiments of the present invention relate to novel methods forforming memory devices. When describing the inventive structures andmethods, the following terms have the following meanings, unlessotherwise indicated.

As used herein, the term “memory device” means a structure in which theelectrical state of which can be altered and then retained in thealtered state; in this way a bit of information can be stored.

“Electrically conductive” and/or “electrically communicating” as usedthrough the present disclosure means a material having a roomtemperature conductivity of greater than 10⁻⁸ (Ω-m)⁻¹.

The term “electrical contact” denotes contact between two materials,wherein the interface between the two materials is electricallyconductive.

The term “abutting” means that a first material contacts a secondmaterial.

The terms “overlying”, “atop”, “positioned on” or “positioned atop”means that a first element, such as a first structure, e.g. a firstlayer, is present on a second element, such as a second structure, e.g.a second layer, wherein intervening elements, such as an interfacestructure, e.g. interface layer, may be present between the firstelement and the second element.

The term “direct physical contact” means that a first element, such as afirst structure, e.g., first phase change material, and a secondelement, such as a second structure, e.g., second phase change material,are connected without any intermediary conducting, insulating orsemiconducting layers at the interface of the two materials.

As used herein, a “metal” is an electrically conductive material,wherein in metal atoms are held together by the force of a metallicbond; and the energy band structure of metal's conduction and valencebands overlap, and hence, there is no energy gap.

As used herein, a “phase change material” denotes a material thatconverts from an amorphous phase to a crystalline phase upon theapplication of energy.

As used herein, a “phase change memory cell” means a structure includingat least one phase change material that is interposed between twocontacts, where at least a portion of the phase change material can beswitched from an amorphous state into a crystalline state, andvise-versa, by application of energy, wherein the crystalline state hasa lower resistivity than the amorphous state.

“Phase resistivity” as used to compare the resistivity of the firstphase change material and the second phase change material means thatthe resistivity of one of the phase change materials is compared to theother of the phase change materials when both phase change materialshave substantially the same microstructure, i.e., when both phase changematerials are in a substantially crystalline phase or when both phasechange materials are in a substantially amorphous phase.

As used herein, the term “pure Ge₂Sb₂Te₅” means a phase change materialcomposed solely of Ge, Sb, and Te with only incidental impurities orless.

“Incidental impurities” means elements that are present in less than 0.5atomic wt. %.

As used herein, the term “doped” means a concentration of an elementthat is purposely provided in a base material, wherein the dopantconcentration may range from about 1 atomic wt. % to about 15 atomic wt.%.

As used herein, a “barrier metal” is a material used to chemicallyisolate the phase change material from other materials and provides anelectrical contact between them.

As used herein, the terms “insulating” and “dielectric” denote amaterial having a room temperature conductivity of less than about 10⁻¹⁰(Ω-m)⁻¹.

References in the specification to “one embodiment”, “an embodiment”,“an example embodiment”, etc., indicate that the embodiment describedmay include a particular feature, structure, or characteristic, butevery embodiment may not necessarily include the particular feature,structure, or characteristic. Moreover, such phrases are not necessarilyreferring to the same embodiment. Further, when a particular feature,structure, or characteristic is described in connection with anembodiment, it is submitted that it is within the knowledge of oneskilled in the art to affect such feature, structure, or characteristicin connection with other embodiments whether or not explicitlydescribed.

For purposes of the description hereinafter, the terms “upper”, “lower”,“right”, “left”, “vertical”, “horizontal”, “top”, “bottom”, “beneath”,“underlying”, “below”, “overlying” and derivatives thereof shall relateto the invention, as it is oriented in the drawing figures.

FIG. 1A depicts one embodiment of a memory device 100, in accordancewith the present invention. In one embodiment, the inventive memorydevice 100 includes a first phase change material 30 having a singularwidth W₁; and a second phase change material 40 comprising a firstportion 40 a that is in direct physical contact with the first phasechange material 30 and having a first width W₂ substantially equal tothe singular width W₁ of the first phase change material 30, and asecond portion 40 b having a second width W₃ greater than the firstwidth W₂ of the first portion 40 a of the second phase change material40, wherein the second phase change material 40 has a greater phaseresistivity than the first phase change material 30.

FIG. 1B depicts another embodiment of the memory device 100 of thepresent invention, wherein an interface barrier metal 35 is positionedbetween, i.e., positioned on, the first phase change material 30 and thesecond phase change material 40. The interface barrier metal 35 may bein direct physical contact with at least one of the first phase changematerial 30 and the second phase change material 40. In one embodiment,the interface barrier metal 35 is in direct physical contact with bothof the first and the second phase change materials 30, 40. Inembodiment, the inventive memory device 100 includes a first phasechange material 30 having a singular width W₁ and interface barriermaterial 35 having a width substantially equal to the singular width W₁of the first phase change material 30. In this embodiment of the presentinvention, the second phase change material 40 includes a first portion40 a that is in direct physical contact with the interface barrier metal35 and has a first width W₂ that is substantially equal to the singularwidth W₁ of the first phase change material 30 and the interface barriermetal 35, and a second portion 40 b having a second width W₃ that isgreater than the first width W₂ of the first portion 40 a of the secondphase change material 40, wherein the second phase change material 40has a greater resistivity than the first phase change material 30.

FIG. 1C depicts another embodiment of the inventive memory device 100.In one embodiment, the inventive memory device 100 includes a firstphase change material 30 having a singular width W₁; and a second phasechange material 40 comprising a first portion 40 a in direct physicalcontact with the first phase change material 30 and having a first widthW₂ substantially equal to the singular width W₁ of the first phasechange material 30. The components shown and labeled in FIGS. 1A-1C willbe described in more detail referring to FIGS. 2A-6.

FIGS. 2A-6 depicts one embodiment of the present method for a memorydevice. FIG. 2A depicts one embodiment of a first dielectric layer 1including at least one conductive structure 10, i.e. electricallyconductive structure, that is positioned atop a substrate 2, such as asemiconducting wafer. In one embodiment, the present method may beginfollowing front end of the line (FEOL) processing, in which the firstdielectric layer 1 is provided as part of an interlevel dielectric layerhaving a plurality of openings that are filled with at least oneconductive material to provide conductive structures 10, which mayinclude but is not limited to metal studs and/or metal bars. In oneembodiment, the first dielectric layer 1 may include a conductivestructure 10 that provides electrical conductivity to a first terminal(source/drain) of a select/access transistor (not shown) that is formedin the underlying substrate 2. In one embodiment, the first dielectriclayer 1 may also include at least one metal bar, wherein the metal baris a conducting line that may be used to provide electrical conductivityto the second (source/drain) terminal of an select/access transistor(not shown) positioned in the underlying substrate 2. In one embodiment,the first dielectric layer 1 may further include a lower conductive line3. The lower conductive line 3 may be a word line, which may bias thegate of the select/access transistor that links the stud with the metalbar. The substrate 2 may include any number of active and/or passivedevices (or regions) located within the substrate 2 or on a surfacethereof. For clarity, the active and/or passive devices (or regions) arenot shown in the drawings, but are nevertheless meant to be includedwith substrate 2.

The substrate 2 may include any semiconductor material including, butnot limited to: Si, Ge, SiGe, SiC, SiGeC, InAs, GaAs, InP and otherIII/V compound semiconductors. The substrate 2 may be undoped, or doped.In one example, the doping of a Si-containing substrate may be light(having a dopant concentration of less than 1E17 atoms/cm³) or heavy(having a dopant concentration of about 1E17 atoms/cm³ or greater). Thesubstrate 2 can have any crystallographic orientation such as (100),(110) or (111). Hybrid substrates having at least two planar surfaces ofdifferent crystallographic orientation are also contemplated.

In one embodiment, the first dielectric layer 1 is formed atop thesubstrate 2 using deposition. More specifically, in one embodiment ofthe invention, the first dielectric layer 1 is formed atop the substrate2 by a deposition process including, for example, chemical vapordeposition (CVD), plasma-assisted CVD, evaporation, spin-on coating, orchemical solution deposition. The first dielectric layer 1 includes anysuitable insulating material that is typically employed in providingvias for interconnects to electrical devices. This includes inorganicdielectrics, organic dielectrics and combinations thereof, including,multilayers thereof. Illustrative examples of suitable materials for thefirst dielectric layer 1 include, but are not limited to: SiO₂, BoronPhospho Silicate Glass (BPSG) oxide, fluorinated SiO₂, Si₃N₄, organicthermoset or thermoplastic dielectrics such as polyimides, polyarylenes,benzocyclobutenes and the like, spun-on glasses including organosilicateglass (OSG), with or without porosity, such as hydrogen silsesquixoane,methyl silsesquixoane, tetraethylorthosilicate (TEOS) and the like,amorphous alloys of Si, O, C and H, or SiCOH, amorphous alloys of Si, O,F and H.

In one embodiment, the first dielectric layer 1 comprises a low-kdielectric having a thickness ranging from about 10 nm to about 1000 nm.A low-k dielectric has a dielectric constant less than the dielectricconstant of SiO₂. In another embodiment, the first dielectric layer 1has a thickness of the order of about 300 nm. In one embodiment, thedielectric constant of the first dielectric layer 1 may be less thanabout 3.5. In another embodiment, the first dielectric layer 1 may rangefrom about 1.0 to about 3.0. Low-k dielectrics may include organicdielectrics such as low dielectric constant polymer dielectrics or mayinclude low dielectric constant carbon-doped oxides. One example of alow-k dielectric polymer dielectric is SiLK™ (trademark of The DowChemical Company). Specifically, SiLK™ is a class of polymer-based low-kdielectric materials comprising a b-staged polymer having a compositionincluding about 95% carbon. An example of a low dielectric constantcarbon doped oxide is SiCOH.

After forming the first dielectric layer 1 on a surface of the substrate2, openings are formed into the first dielectric layer 1 so as to exposeportions of the underlying substrate 2, in which conductive structures10, such as metal studs and/or metal bars are subsequently formed. Inone embodiment, the openings are provided with a circular cross sectionwhen viewed from the top view. The openings, hereafter referred to asvias, are formed utilizing lithography and etching. For example, thelithographic step may include applying a photoresist to the firstdielectric layer 1, exposing the photoresist to a pattern of radiationand developing the pattern into the exposed photoresist utilizing aresist developer. In one embodiment, the etching step used in formingthe vias into first dielectric layer 1 may include reactive ion etching(RIE), plasma etching, ion beam etching or laser ablation. Followingetching, the photoresist is typically removed from the structureutilizing a resist stripping process, such as oxygen ashing.

In one embodiment, conductive structures 10, such as metal studs andbars, are then formed within the vias in the first dielectric layer 1using deposition and planarization processes. In one embodiment, aconductive material, such as Cu or W, may be formed within the viasutilizing a deposition process, such as plating or sputtering, fillingat least the vias to provide the conductive structures 10. After fillingthe vias with a conductive material, the structure may be subjected to aplanarization process, such as chemical-mechanical polishing and/orgrinding, to provide a planar structure.

In one embodiment, an electrically conductive liner is positionedbetween the conductive structures 10 and the via sidewalls. In oneembodiment, the electrically conductive liner may comprise TiN or TaN.In one embodiment, the electrically conductive liner may have athickness ranging from about 2 nm to about 50 nm. In one embodiment, theelectrically conductive liner may be deposited by sputter deposition orby chemical vapor deposition.

Still referring to FIG. 2A, in one embodiment, following the formationof the conductive structures 10, a layered stack 12 is formed atop theupper surface of the first dielectric layer 1 and atop the upper surface11 of the conductive structures 10. In one embodiment, the layered stack12 includes a layer of a first barrier metal 15 atop the upper surfaceof the first dielectric layer 1 and the upper surface 11 of theconductive structures 10; a layer of a first phase change material 30atop the upper surface of the layer of the first barrier metal 15; and alayer of a sacrificial material 16, which may be an barrier material,atop the upper surface 31 of the layer of the first phase changematerial 30.

Referring to FIG. 2B, in another embodiment of the present invention inwhich a interface barrier metal 35 is positioned between the first phasechange material 30 and the second phase change material 40, the layeredstack 12 that is formed atop the upper surface of the first dielectriclayer 1 and the conductive structures 10 includes a layer of a firstbarrier metal 15 atop the upper surface of the first dielectric layer 1and the upper surface 11 of the conductive structures 10; a layer of afirst phase change material 30 atop the upper surface of the layer ofthe first barrier metal 15; and an interface barrier metal 35 atop theupper surface 31 of the layer of the first phase change material 30.

In one embodiment, the layer of the first barrier metal 15 or theinterface barrier metal 35 is TiN, TaN or a combination thereof. In oneembodiment, the layers of the first barrier metal 15 and the interfacebarrier metal 35 are blanket deposited by a physical deposition process(PVD), such as sputtering. In another embodiment, the layer of the firstbarrier metal is and/or the layer of the interface barrier metal 35 maybe deposited by chemical vapor deposition (CVD). In one embodiment, thelayer of first barrier metal 15 may have a thickness ranging from about0 nm to about 100 nm. In one embodiment, the layer of the interfacebarrier metal 35 may have a thickness ranging from about 20 nm to about100 nm. In one embodiment, the first phase change material 30 is byconstruction in the crystalline state and remains in the crystallinestate to serve as the lower electrode to the memory device 100. In oneembodiment in which the first phase change material 30 remains in thecrystalline state and first phase change material 30 functions as thelower electrode to the memory device, the first phase change material 30is in direct physical contact with the second phase change material 40.In another embodiment, in which the interface barrier metal 35 ispresent, the interface barrier metal 35 serves as the lower electrode tothe memory device 100. In one embodiment when the interface barriermetal 35 functions as the lower electrode, the interface barrier metal35 is in direct physical contact with the second phase change material40.

In one embodiment, the first phase change material 30 may be composed ofan essentially pure phase change material composition. For example, inone embodiment, the first phase change material 30 may be composed ofGe₂Sb₂Te₅ (GST) without any purposeful additional of oxide, nitride oroxynitride dopants. In another embodiment, the first phase changematerial 30 may be composed of a GeSb alloy. In one embodiment when thefirst phase change material 30 is a GeSb alloy, the composition of theGeSb alloy is approximately Ge₈Sb₁₂. In one embodiment, the resistivityof the first phase change material 30 ranges from about 10⁻⁶ ohm-m toabout 10² ohm-m. In one embodiment, the thermal conductivity of thefirst phase change material 30 ranges from about 0.02 W/mK to about 2W/mK.

The first phase change material 30 may be switched from an amorphousphase to a crystalline phase. In one embodiment, when in an amorphousstate, the first phase change material 30 exhibits a high resistivity,typically ranging from about 10⁻² ohm-m to about 10² ohm-m. In oneembodiment, when in a crystalline state, the first phase change material30 is more conductive, exhibiting a lower room temperature resistivitytypically ranging from about 10⁻⁶ ohm-m to about 10⁻⁴ ohm-m.

It is noted that other materials have been contemplated for the firstphase change material 30 and are within the scope of the presentinvention, so long as the material selected for the first phase changematerial 30 provides a lower resistivity in the crystalline state thanthe material selected for the second phase change material 40 in thecrystalline state. For example, in one embodiment, the first phasechange material 30 may comprise chalcogenide alloys. The termchalcogenide is used herein to denote an alloy or compound material,which contains at least one element from Group VI of the Periodic Tableof Elements. Illustrative examples of chalcogenide alloys that can beemployed for the first phase change material 30 may include, but are notlimited to, alloys of Te or Se with at least one of the elements of Ge,Sb, As, Si. In other embodiments, the first phase change material 30 maybe composed of any suitable material including one or more of theelements Te, Ga, In, Se, and S. Although chalcogenides are a group ofmaterials commonly utilized as phase change material, some phase changematerials, such as GeSb (GS), do not utilize, chalcogenides and in someembodiments of the present invention may be equally suitable for thefirst phase change material 30. Thus, a variety of materials can be usedin a first phase change material 30 so long as they can retain separateamorphous and crystalline states of distinct resistivity.

In one embodiment, the first phase change material 30 is composed of GSTand is in an amorphous phase when at a temperature of about 25° C. Asthe temperature of the first GST phase change material 30 is increasedto about 125° C. to about 150° C., the resistivity of the first GSTphase change material 30 decreases representing the transitiontemperature for a phase change from an amorphous phase to Face CenterCubic (FCC) phase. Further increases in the temperature of the first GSTphase change material 30 to greater than about 180° C. result in furtherdecreases in resistivity, which result from a phase change from the FaceCentered Cubic (FCC) phase to a Hexagonal (Hex) phase of the first phasechange material 30. When the temperature of the first GST phase changematerial 30 is increased above the melting temperature (i.e., 620° C.),the first GST phase change material 30 melts and upon quench returns tothe amorphous solid phase. The term “quench” denotes solidification in atime period on the order of about 0.5 to about 50 nanoseconds.

In at least one embodiment of the present invention, the phase changematerials, i.e. first phase change material 30 and second phase changematerial 40, are in the crystalline state prior to the cycling of thememory cell 100 due to the typical processing temperatures that are usedto construct the memory cell 100. In at least one embodiment of thepresent invention, because of the lower resistivity of the first phasechange material 30 compared to that of the second phase change material40, the first phase change material 30 remains in the crystalline stageduring memory cell 100 operation, since the power is dissipated mainlyin the second phase change material 40. Furthermore, in at least oneembodiment of the invention, the first phase change material 30 providesthermal insulation for the memory cell 100 while preserving conductivityto the second phase change material 40 so that the rest power isreduced.

The layer of the first phase change material 30 may be deposited atopthe layer of the first barrier layer 15 using physical vapor deposition(PVD), such as sputtering, or may be deposited by chemical vapordeposition. Chemical Vapor Deposition (CVD) is a deposition process inwhich a deposited species is formed as a result of chemical reactionbetween gaseous reactants at greater than room temperature (25° C. to600° C.); wherein solid product of the reaction is deposited on thesurface on which a film, coating, or layer of the solid product is to beformed. Variations of CVD processes include, but not limited to,Atmospheric Pressure CVD (APCVD), Low Pressure CVD (LPCVD) and PlasmaEnhanced CVD (EPCVD), Metal-Organic CVD (MOCVD) and combinations thereofmay also be employed. In one embodiment, the layer of the first phasechange material 30 may have a thickness ranging from about 20 nm toabout 200 nm.

In one embodiment, the layer of sacrificial material 16 that ispositioned atop the layer of the first phase change material 30 is abarrier metal, such as TiN or TaN, In one embodiment, the layer of thesacrificial material 16 is blanket deposited by a physical depositionprocess, such as sputtering. In another embodiment, the sacrificialmaterial 16 may be deposited by chemical vapor deposition. In oneembodiment, the sacrificial material 16 may have a thickness rangingfrom about 20 nm to about 200 mm. It is noted that other materials thatare not reactive with the phase change material, i.e. first phase changematerial 30, have been contemplated for the sacrificial material 16 andare within the scope of the present invention. For example, thesacrificial material 16 may be a nitride. In one embodiment, thesacrificial material 16 functions to protect the first phase changematerial 30 from the chemistry of a subsequently conducted lithographyprocess or acts as hard mask during a subsequently conducted etchprocesses, such as reactive ion etch (RIE).

In the embodiments of the present invention that include the interfacebarrier metal 35 positioned between the first phase change material 30and the second phase change material 40, as depicted in FIGS. 1B and 2B,the interface barrier metal 35 is deposited atop the layer of the firstphase change material 30, and is composed of a barrier metal, such asTiN or TaN. In one embodiment, the layer of the interface barrier metal35 is blanket deposited by a physical deposition process (PVD), such assputtering. In another embodiment, the layer of the interface barriermetal 35 is deposited by chemical vapor deposition (CVD). In oneembodiment, the interface barrier metal 35 has a thickness ranging fromabout 20 nm to about 200 nm. It is noted that other materials that arenon-reactive with phase change materials, i.e., the first phase changematerial 30 and the second phase change material 40, have beencontemplated for the interface barrier metal 35 and are within the scopeof the present invention.

In one embodiment following the formation of the layer of thesacrificial material 16, as depicted in FIG. 2A, or the layer of theinterface barrier metal 35, as depicted in FIG. 2B, a pillar 33, asshown in FIG. 3, is formed utilizing photolithography and etchprocesses. It is noted that although FIGS. 3-6 depict the sacrificialmaterial 16, and not the layer of the interface barrier metal 35, thatFIG. 3-6 are equally applicable to the embodiments of the invention thatinclude the interface barrier metal 35 and the embodiments of theinvention in which the interface barrier metal 35 is omitted.

As used herein, a pillar is a structure that provides the dimensions fora subsequently formed cavity, which may also be referred to as a pore.More specifically, in one embodiment, a block mask 32 is formed atop aportion of the layer of the sacrificial material 16, or the interfacemetal barrier 35, wherein a remaining portion of the sacrificialmaterial 16 is exposed. In one embodiment, the block mask 32 may beformed from a photoresist layer. In another embodiment, the block mask32 may be provided by a hard mask.

Referring to FIGS. 2A and 2B, following block mask 32 formation, theexposed portion of the sacrificial material 16, or the exposed portionof the interface barrier metal 35, and the portions of the first phasechange material 30 and first barrier metal 15 underlying the exposedportion of the sacrificial material 16, or the exposed portion of theinterface barrier metal 35, are removed by an anisotropic etch step toprovide the pillar 33. In one embodiment, the anisotropic etch stepincludes a first etch step for removing the exposed portions of thesacrificial material 16, or the interface barrier metal 35, selective tothe first phase change material 30; a second etch step for removing thefirst phase change material 30 selective to the first barrier metal 15;and a third etch step for removing the first barrier metal 15 selectiveto the first dielectric layer 1 and the conductive region 10. In anotherembodiment of the present invention, the above described first, secondand third etch steps for providing the pillar 33 each include a similaretch chemistry.

In one embodiment, width W₄ of the conductive structure 10 is greaterthan the width W₁ of the pillar 33. In one embodiment, the width W₄ ofthe conductive structure 10 ranges from about 90 nm to about 400 nm. Inanother embodiment, the width W₄ of the conductive structure 10 rangesfrom about 45 nm to about 250 nm. In yet another embodiment, the widthW₄ of the conductive region 10 ranges from about 22 nm to about 100 nm.In one embodiment, the width W₁ of the pillar 33 ranges from about 40 nmto about 100 nm. In another embodiment, the width W₁ of the pillar 33ranges from about 30 nm to about 60 nm. In a further embodiment, thewidth W₁ of the pillar 33 ranges from about 10 nm to about 40 nm. It isnoted that embodiments of the present invention have been contemplatedin which the pillar 33 is provided without the first barrier metal 15,wherein the block mask 32 is formed atop the layer of the sacrificiallayer 16 or barrier contact 160. Following the formation of the pillar33, the block mask 32 may be removed by an oxygen ash.

FIG. 3 depicts one embodiment of forming an insulating material 50 atopat least the exposed portions of the conductive structure 10 adjacentthe portion of the conductive structure 10 on which the pillar 33 ispositioned, wherein an upper surface 51 of the insulating material 50 isplanarized to be substantially co-planar with an upper surface 34 of thepillar 33. In one embodiment, the insulating material 50 may be anoxide, nitride, oxynitride or combination thereof. In one embodiment,the insulating material 50 is an oxide that is deposited by chemicalvapor deposition. In one embodiment, the insulating material may becomposed of high density plasma (HDP) chemical vapor deposition (CVD)deposited silicon oxide having a thickness ranging from about 10 nm toabout 300 nm. HDPCVD is a chemical vapor deposition process thatutilizes a low pressure (2-10-mTorr range) to achieve a high electrondensity (10¹⁰ cm³-10¹² cm³) and a high fractional ionization rate (10⁻⁴to 10⁻¹) for deposition.

Following deposition, the insulating material 50 may be planarized toexpose the upper surface of the first phase change material 30, or theupper surface of the interface barrier metal 35. Planarization is amaterial removal process that employs at least mechanical forces, suchas frictional media, to produce a planar surface. In one embodiment, theinsulating material 50 may be planarized by chemical mechanicalpolishing (CMP). Chemical Mechanical Planarization is a material removalprocess using both chemical reactions and mechanical forces to removematerial and planarize a surface. In one embodiment, the insulatingmaterial 50 is planarized until the upper surface 34 of the first phasechange material 30 of the pillar 33 is exposed.

FIG. 4 is a side cross sectional view depicting recessing of the uppersurface 34 of the first phase change material 30 of the pillar 33 belowan upper surface 51 of the insulating material 50 to provide a recessedfirst phase change material 30 a, in accordance with one embodiment ofthe present invention. In one embodiment, the upper surface 34 of thefirst phase change material 30 is etched using an anisotropic etchprocess, i.e., Reactive Ion Etching (RIE), selective to the insulatingmaterial 50. In one embodiment, the first phase change material 30 iscomposed of high purity Ge₂Sb₂Te₅ and the insulating material iscomposed of SiO₂, recessing the first phase change material 30 includesreactive ion etch processing with a chlorine containing plasma, such asCl₂/Ar. In another embodiment, the reactive ion etch chemistry may be afluorine containing plasma, such as CF₄/CHF₃/Ar. In another embodiment,the upper surface 34 of the first phase change material 30 is etchedusing a wet chemistry, such as diluted hydrofluoric acid (DHF). In oneembodiment, the etch process is a timed etch. In one embodiment, theupper surface 30 b of the recessed first phase change material 30 a isat a depth ranging from about 10 nm to about 180 nm from the uppersurface 51 of the insulating material 50 to provide a cavity 52. Inanother embodiment, the recessed first phase change material 30 a is ata depth ranging from about 10 nm to about 80 nm from the upper surface51 of the insulating material 50. In a further embodiment, the recessedfirst phase change material 30 a is at a depth ranging from about 10 nmto about 50 nm from the upper surface 51 of the insulating material 50.It is noted that although the first barrier metal 15 is depicted in thesupplied figures, the first barrier metal 15 is optional, andembodiments of the present invention have been contemplated, in whichthe barrier metal 15 has been omitted.

In at least one of the embodiments of the present invention that includethe interface barrier material 35 between the first phase changematerial 30 and the second phase change material 40, the interfacebarrier metal 35 atop the first phase change material 30 of the pillar33 is recessed with an etch process selective to the upper surface 51 ofthe insulating material 50 using a Cl₂/Ar chemistry.

FIG. 5 is a side cross sectional view depicting the formation of asecond phase change material 40 atop the recessed first phase changematerial 30 a and the upper surface 51 of the insulating material 50, inaccordance with at least one embodiment of the present invention.Similar to the first phase change material 30, the second phase changematerial 40 may be switched from an amorphous phase to a crystallinephase. In one embodiment, the second phase change material 40 may becomposed of Ge₂Sb₂Te₅ that is doped with dopants composed of oxides,nitrides, oxynitride or combinations thereof. In one embodiment, thesecond phase change material 50 may be composed of Ge₂Sb₂Te₅ includingSi₃N₄ or SiO₂ dopants present in approximately 5 wt. % to approximately10 wt. %.

In one embodiment, the second phase change material 40 may be depositedby physical vapor deposition (PVD), such as sputtering, or chemicalvapor deposition (CVD). In one embodiment, the dopant may be introducedto the second phase change material 40 during the deposition process. Insome embodiments of the present invention, the dopants may be added tothe second phase change material 40 utilizing at least one of ionimplantation, gas phase doping, dopant out diffusion or a combinationthereof. In one embodiment, the second phase change material 40 may becomposed of Ge₂Sb₂Te₅ doped with Si₃N₄ or SiO₂ dopants, wherein theGe₂Sb₂Te₅ is co-sputtered with the dopant. Dopants can be includedeither in the primary target, or co sputtered from other targets. In oneembodiment, the room temperature resistivity of the second phase changematerial layer 40 ranges from about 10⁻² ohm-m to about 10⁺⁵ ohm-m.

Similar to the first phase change material 30, when in an amorphousstate the second phase change material 40 exhibits a high resistivity,typically ranging from about 1 ohm-m to about 10³ ohm-m. In oneembodiment, when in a crystalline state, the second phase changematerial 40 is more conductive, exhibiting a lower resistivity typicallyranging from about 10⁻² ohm-m to about 1 ohm-m.

It is noted that other materials have been contemplated for the secondphase change material 40 and are within the scope of the presentinvention, so long as the material selected for the second phase changematerial 40 provides a lower resistivity than the material selected forthe first phase change material 30. For example, in one embodiment, thesecond phase change material 40 may comprise chalcogenide alloys.Illustrative examples of chalcogenide alloys that can be employed forthe second phase change material 40 include, but are not limited to,alloys of Te or Se with at least one of the elements of Ge, Sb, As, Si.In other embodiments, the second phase change material 40 is composed ofany suitable material including one or more of the elements Te, Ga, In,Se, and S, so long as the material is capable of phase change and has aresistivity greater than the first phase change material 30. It is notedthat the second phase change material 40 may be composed of anon-chalcogenide material, such as GeSb. Thus, a variety of materialscan be used for the second phase change material 40 so long as they canretain separate amorphous and crystalline states of distinctresistivity, and have a resistivity greater than the first phase changematerial 30.

In one embodiment, the second phase change material 40 is composed ofdoped Ge₂Sb₂Te₅ (GST) and is in an amorphous phase when at a temperatureof about 25° C. As the temperature of the second GST phase changematerial 40 is increased to about 180° C. to about 280° C., theresistivity of the phase change material decreases representing thetransition temperature for a phase change from an amorphous phase toFace Center Cubic (FCC) phase. Further increases in the temperature ofthe second GST phase change material to greater than about 180° C.result in further decreases in resistivity, which result from a phasechange from the Face Centered Cubic (FCC) phase to a Hexagonal (Hex)phase of the second phase change material 40. When the temperature ofthe second GST phase change material 40 is increased above the meltingtemperature (620° C.), the second GST phase change material 40 melts andupon quench returns to the amorphous solid phase.

In one embodiment, the second phase change material 40 may be depositedatop the recessed first phase change material 30 a using a singledeposition and planarization step. For example, in one embodiment, thesecond phase change material 40 is deposited to fill the cavity 52 andextend atop the upper surface 51 of the insulating material 50, whereinfollowing deposition a planarization step, such as CMP, is conducted toprovide a second phase change material 40 having a planar upper surface.The first portion 40 a of the second phase change material 40 may becontained within the via. The second portion 40 b of the phase changematerial 40 may be positioned atop the first portion 40 a of the phasechange material 40 and extends atop the insulating material 50. Inanother embodiment, the planarization step is omitted.

In another embodiment, the second phase change material 40 may bedeposited using a two step deposition and planarization process. Forexample, in a first deposition step the first portion 40 a of the secondphase change material 40 may be deposited to fill the cavity 52, whereinthe portion of the second phase change material 40 a within the cavity52 is planarized to provide an upper surface substantially coplanar tothe insulating material 50. Thereafter, a second layer of the secondphase change material 40 is deposited atop the coplanar upper surface ofthe insulating material 50 and the second phase change material 40within the cavity 52 to provide the second portion 40 b of the secondphase change material 40.

In another embodiment, the second phase change material 40 may bedeposited using a single deposition and planarization process. Forexample, in a first deposition step the second phase change material 40may be deposited to fill the cavity 52, wherein the portion of thesecond phase change material 40 a within the cavity 52 is planarized toprovide an upper surface substantially coplanar to the insulatingmaterial 50, as depicted in FIG. 1C.

Referring to FIG. 5, in a following process step the second barriermetal 65 may be optionally deposited top the second phase changematerial 40. The second barrier metal 65 may be TiN, TaN or acombination thereof. In one embodiment, the second barrier metal 65 isblanket deposited by a physical vapor deposition (PVD) process, such assputtering. In another embodiment, the second barrier metal 65 may bedeposited by chemical vapor deposition (CVD). In one embodiment, thesecond barrier metal 65 may have a thickness ranging from about 20 nm toabout 200 nm.

In a following step, an upper electrode 70 may be formed atop the secondbarrier metal 65. The upper electrode 70 is formed by physical vapordeposition, such as plating or sputtering. In one embodiment, the upperelectrode 70 is composed of tungsten, copper, aluminum, silver, gold andmultilayers and alloys thereof. In one embodiment, the upper electrode70 may have a thickness ranging from about 100 nm to about 700 nm. Inone embodiment, the upper electrode 70 may further include a silicidesurface (not shown).

Following formation of the upper electrode 70, a passivation layer 80 ofdielectric material is blanket deposited atop the entire structure andplanarized, as depicted in FIG. 6. The passivation layer 80 may beselected from the group consisting of silicon-containing materials suchas SiO₂, Si₃N₄, SiOxNy, SiC, SiCO, SiCOH, and SiCH compounds; theabove-mentioned silicon-containing materials with some or all of the Sireplaced by Ge; carbon-doped oxides; inorganic oxides; inorganicpolymers; hybrid polymers; organic polymers such as polyamides or SiLK™;other carbon-containing materials; organo-inorganic materials such asspin-on glasses and silsesquioxane-based materials; and diamond-likecarbon (DLC, also known as amorphous hydrogenated carbon, a-C:H).

The passivation layer 80 may be formed by various methods including butnot limited to: spinning from solution, spraying from solution, chemicalvapor deposition (CVD), plasma enhanced CVD (PECVD), sputter deposition,reactive sputter deposition, ion-beam deposition, and evaporation. Thepassivation layer 80 may then patterned and etched to forth via holes(not shown) to the various source/drain and gate conductor regions ofthe substrate. Following via formation, interconnects (not shown) areformed by depositing a conductive metal into the via holes usingconventional processing, such as CVD or plating. The conductive metalmay include, but is not limited to: tungsten, copper, aluminum, silver,gold, and alloys thereof.

While the present invention has been particularly shown and describedwith respect to the preferred embodiments thereof it will be understoodby those skilled in the art that the foregoing and other changes informs of details may be made without departing form the spirit and scopeof the present invention. It is therefore intended that the presentinvention not be limited to the exact forms and details described andillustrated, but fall within the scope of the appended claims.

1. A method of manufacturing an electrode comprising: providing a pillarof at least a first phase change material positioned on a conductivestructure positioned in a dielectric layer, wherein the first phasechange material includes at least one of Te, Ga, In, Se and S; formingan insulating material abutting the pillar of the first phase changematerial and atop the conductive structure, wherein an upper surface ofthe insulating material is coplanar with an upper surface of the pillar;recessing the upper surface of the pillar below the upper surface of theinsulating material to provide a recessed pillar; and forming a secondphase change material atop the recessed pillar and the upper surface ofthe insulating material, the second phase change material includes atleast one of Te, Ga, In, Se and S, wherein the second phase changematerial has a greater phase resistivity than the first phase changematerial.
 2. The method of claim 1, wherein the first phase changematerial is in direct physical contact with the second phase changematerial.
 3. The method of claim 1, wherein the pillar further comprisesa first barrier metal positioned between the first phase change materialand the conductive structure.
 4. The method of claim 1, wherein theconductive structure has a greater width than the pillar.
 5. The methodof claim 1, wherein the providing of the pillar comprises: depositing alayer of the first barrier metal atop the conductive structure and thedielectric layer; depositing a layer of the first phase change materialatop the layer of the first barrier metal; forming a block mask atop aportion of the layer of the first phase change material, wherein aremaining portion of the layer of the first phase change material isexposed; removing the remaining portion of the layer of the first phasechange material and portions of the first barrier metal underlying theremaining portion of the layer of the first phase change material withan anisotropic etch step; and removing the block mask.
 6. The method ofclaim 1, wherein the first phase change material comprises high purityGe₂Sb₂Te₅.
 7. The method of claim 1, wherein the recessing of the uppersurface of the pillar below the upper surface of the insulating materialto provide the recessed pillar comprises etching the first phase changematerial selective to the insulating material until the upper surface ofthe pillar is recessed to a depth below the upper surface of theinsulating material to provide a cavity atop a recessed first phasechange material.
 8. The method of claim 7, wherein the step of theforming of the second phase change material atop the recessed firstphase change material and the upper surface of the insulating materialcomprises: depositing a first layer of the second phase change materialatop the recessed phase change material and the insulating material; andforming a second barrier metal atop the second phase change material. 9.The method of claim 7, wherein the step of the forming of the secondphase change material atop the recessed first phase change material andthe upper surface of the insulating material comprises: depositing afirst layer of the second phase change material atop the recessed phasechange material and the insulating material; planarizing the first layerof the second phase change material until an upper surface of the secondphase change material within the cavity is coplanar with the uppersurface of the insulating material; depositing a second layer of thephase change material atop the upper surface of the second phase changematerial within the cavity and the upper surface of the insulatingmaterial; and forming a second barrier metal atop the second phasechange material.
 10. The method of claim 1, wherein the second phasechange material comprises Ge₂Sb₂Te₅ doped with a nitride, oxide, oroxynitride.
 11. A method of manufacturing an electrode comprising:providing a pillar of at least a first phase change material positionedon a conductive structure positioned in a dielectric layer; forming aninsulating material abutting the pillar of the first phase changematerial and atop the conductive structure, wherein an upper surface ofthe insulating material is coplanar with an upper surface of the pillar;recessing the upper surface of the pillar below the upper surface of theinsulating material to provide a recessed pillar; forming an interfacebarrier metal on an upper surface of the first phase change material ofthe recessed pillar; and forming a second phase change material atop theinterface barrier metal of the recessed pillar and the upper surface ofthe insulating material, wherein the second phase change material has agreater phase resistivity than the first phase change material.
 12. Themethod of claim 11, wherein the interface barrier metal is in directphysical contact with the first phase change material and the secondphase change material.
 13. The method of claim 11, wherein the providingof the pillar comprises: depositing a layer of the first phase changematerial atop the layer of the first barrier metal; depositing a layerof the interface barrier metal atop the layer of the first phase changematerial; forming a block mask atop a portion of the layer of theinterface barrier metal, wherein a remaining portion of the layer of theinterface barrier metal is exposed; removing the remaining portion ofthe layer of the interface barrier metal and portions of the first phasechange material and first barrier metal underlying the remaining portionof the layer of interface barrier metal with an anisotropic etch step;and removing the block mask.
 14. The method of claim 11, wherein thefirst phase change material is a GeSb alloy.
 15. The method of claim 11,wherein the recessing of the upper surface of the pillar below the uppersurface of the insulating material to provide the recessed pillarcomprises etching the interface barrier metal selective to theinsulating material until the upper surface of the pillar is recessed toa depth below the upper surface of the insulating material to provide acavity atop a recessed interface barrier metal.
 16. The method of claim15, wherein the step of the forming of the second phase change materialatop the recessed interface barrier metal and the upper surface of theinsulating material comprises: depositing a first layer of the secondphase change material atop the recessed interface barrier metal and theinsulating material; planarizing the first layer of the second phasechange material until an upper surface of the second phase changematerial within the cavity is coplanar with the upper surface of theinsulating material; and forming a second barrier metal atop the secondphase change material.
 17. The method of claim 15, wherein the step ofthe forming of the second phase change material atop the recessedinterface barrier metal and the upper surface of the insulating materialcomprises: depositing a first layer of the second phase change materialatop the recessed interface barrier metal and the insulating material;planarizing the first layer of the second phase change material until anupper surface of the second phase change material within the cavity iscoplanar with the upper surface of the insulating material; depositing asecond layer of the phase change material atop the upper surface of thesecond phase change material within the cavity and the upper surface ofthe insulating material; and forming a second barrier metal atop thesecond phase change material.
 18. The method of claim 11, wherein theinterface barrier metal comprises TiN or TaN.